TW574146B - Process for cleaning up wastewaters from an aldolization reaction which is followed by hydrogenation - Google Patents

Abstract

Purification of 3 waste liquor fractions from the production of alcohols by aldol condensation and hydrogenation comprising extraction with 8-16C monoalcohols and/or 6-12C hydrocarbons in which before extraction, at least 2 of the 3 fractions are combined and adjusted to pH 0-6 and the resultant organic phase is optionally separated and 1 or more of the fractions is contacted with a coalescing filter during purification. Purification of waste liquor from the production of alcohols by aldol condensation and hydrogenation, which consists of 3 fractions, comprising: (1) the aqueous phase containing catalyst from aldol condensation; (2) the washing water from the purification of the alpha , beta -unsaturated aldehyde obtained in the aldol condensation stage; and (3) the washing water from the purification of the residue from alcohol distillation. Purification involves extracting the waste liquor with 8-16C monoalcohols and/or 6-12 C hydrocarbons. Before extraction, at least 2 of the 3 fractions are combined and adjusted to pH 0-6, preferably 1-3 and the resultant organic phase is optionally separated and 1 or more of the fractions is contacted with a coalescing filter during purification.

Description

574146574146

五、發明說明（1) 本發明係關於在相同或不同醛類或_類的醇酸化，或 在酸類和顯I類的混合醇醛化，接著加氫所製成廢水之化 方法。 以下所用醇醛化包含醇醛加成和醇醛縮合。醇酿加成 指在酿類或酮類的碳醯基，利用鹼或酸觸媒添加活化亞甲 基’形成3 —經基碳醯化合物。若醇酸加成接著去水，在 使用酸觸媒時容易發生且常用，稱為醇醛縮合。醇駿縮合 的生成物為α，/3 -不飽和碳醯化合物。 同樣醛或同樣酮的二分子醇醛化特別重要。此類反應 亦Τ在工業上利用。工業用途之一例為利用正丁駿的醇^ 化再加氫，以製造2-乙基己醇，此為低級醇類甲醇到丁醇 之後最重要的合成醇。2-乙基己醇的酞酯廣用做塑膠挎 塑劑。 /曰V. Description of the invention (1) The present invention relates to a method for acidification of alcohols in the same or different aldehydes or aldehydes, or a mixed aldolization of acids and significant I, followed by hydrogenation to produce wastewater. The aldolization used below includes aldol addition and aldol condensation. Alcoholic fermentation refers to the addition of activated methylene 'to a carbamate group of a brewery or ketone group by using an alkali or acid catalyst to form a 3-carbocarbamate compound. If the alkyd addition is followed by water removal, it is easy to occur and commonly used when using acid catalysts, and is called aldol condensation. The product of the alcohol condensation is an α, / 3-unsaturated carbohydrate compound. Aldolization of two molecules of the same aldehyde or the same ketone is particularly important. Such reactions are also used industrially. An example of industrial use is the use of n-butanol alcohols and hydrogenation to produce 2-ethylhexanol, which is the most important synthetic alcohol after the lower alcohols methanol to butanol. 2-Ethylhexanol phthalate is widely used as a plastic molding agent. / Say

為了加設醇醛化步驟以製造醇類，原料醛類是在驗水 溶液存在下，先於醇醛縮合中反應，形成α，石―不飽和醛 ’在上述2-乙基己醇製造中，正丁醛即例如在氫氧化鈉水 溶液作用下反應形成2-乙基己醛，包括α，召―不飽和酸的 有機相，再從含觸媒的水相分離。然後，有機相經水洗， 而α，召-不飽和醛即加氫而得所需醇，以2〜乙基·而言， 則得2 -乙基己醇。如此所得粗醇即利用蒸餾精製，此項精 餘殘餘物經進一步水洗。 ' 在醇酿化和隨後加氫過程中，製成三種不同的廢水部 (1)醇醛化反應所得含觸媒水相，In order to add an aldolization step to produce alcohols, the raw material aldehydes are reacted in the presence of an aqueous solution prior to the aldol condensation to form α, stone-unsaturated aldehydes in the above 2-ethylhexanol production, N-butyraldehyde, for example, reacts under the action of an aqueous solution of sodium hydroxide to form 2-ethylhexanal, which includes alpha, an organic phase of an unsaturated acid, and is separated from the aqueous phase containing the catalyst. Then, the organic phase is washed with water, and the α, z-unsaturated aldehyde is hydrogenated to obtain the desired alcohol. In terms of 2 ~ ethyl ·, 2-ethylhexanol is obtained. The crude alcohol thus obtained was purified by distillation, and the residue of this residue was further washed with water. '' In the alcohol fermentation and subsequent hydrogenation process, three different wastewater sections are made (1) the catalyst-containing aqueous phase obtained from the aldolization reaction,

第5頁 574146 五、發明說明（2) (2)醇藤化製成α，/9 -不飽和藤精製所得洗水， (3 )醇蒸餾殘渣淨化所得洗水。 此等廢水部份包括水溶性和非水溶性，因此在工業製 法階段，除未反應原料和製成極少量生成物外，還會形成 乳化的副產品。Page 5 574146 V. Description of the invention (2) (2) Washing water obtained by refining α, / 9-unsaturated rattan with alcohol rattan, (3) Purification water obtained by purifying alcohol distillation residue. These wastewaters include water-soluble and water-insoluble components. Therefore, in the industrial process stage, in addition to unreacted raw materials and a small amount of products, emulsified by-products are formed.

未反應原料係醇醛化的原料醛，諸如正丁盤，而製成 的生成物，係醇盤化的α，万-不飽和盤類，和加氫後由此 $成的醇類。此等生成物相對於廢水總量中醇酸化和加氯 副產品只是極少量。以正丁醛的醇醛化情況而言，例如 乙基己醛存在量頂多為廢水内存在的全部有機化合物總量 即未反應原料、醇备化和加氮副產品，以及醇酸化和加 氫生成物合計之0· 2 %重量。 由所用醛在醇醛化當中形成的副產品主要是: •所用醛類的支鏈異構物 •和醛具有同樣碳數的直鏈或支鏈醇類 •比所用醛多一個碳原子的直鏈或支鏈醇類 •和藤具有同樣碳數的環醋類（内_類） •和醛具有同樣碳數的羧酸，呈鹽存在，尤其是驗金 屬鹽，以及相對應游離羧酸 、The unreacted raw materials are alcohol-formulated raw aldehydes, such as n-butyl plates, and the products produced are alcohol-formulated α, 10,000-unsaturated disks, and alcohols formed by hydrogenation. These products are only a small amount relative to the by-products of alkyd and chlorination in the total wastewater. In terms of the aldolization of n-butyraldehyde, for example, the maximum amount of ethylhexanal is the total amount of all organic compounds present in the wastewater, that is, unreacted raw materials, alcohol preparation and nitrogen addition by-products, and alcohol acidification and hydrogenation. The total product was 0.2% by weight. The by-products formed by the aldehyde used in the aldolization are: • branched isomers of the aldehydes used • straight or branched chain alcohols with the same carbon number as the aldehydes • straight chains with one more carbon atom than the aldehydes used Or branched chain alcohols • Cyclic vinegars (endo) with the same carbon number as rattan • Carboxylic acids with the same carbon number as aldehydes, which are present as salts, especially metal salts, and corresponding free carboxylic acids,

•醇醛化反應所得a，/S -不飽和酿加氫製成的類 •由醇藤化和接著加氫所得比所需醇多4個碳原子 環内酯類和環二醇類 ' 的 •來自所需醇的竣酸酯和相對應羧酸 .來自所需醇並與原料醛碳原子數相對的羧酸酯和羧• A, / S-unsaturated hydrogenated products obtained from aldolization reactions • Hydrogenated and then hydrogenated to obtain 4 more carbon atoms, cyclic lactones and cyclic diols than required alcohols • Esters and corresponding carboxylic acids from the desired alcohol. Carboxylic esters and carboxylic acids from the desired alcohol and the number of carbon atoms in the raw material aldehyde

第6頁 五、發明說明（3) 酸 此I，下列可能以極少量副產σ户 •由醇醛化^7 ο J產。口存在·· 或多1個碳^ ^ ^所需醇少1或2個碳原子 内酯類和酸類。、、 支鏈醇類、醛類、醚類、 此外，廢k 成物，以及沸點=Γ匕括來自醇駿化反應副產品之加氣生 若2乙I 尚之縮合生成物。 化，接著加ί3ί由ΐ:路在氫氧化納溶液存在下醇酿 異丁醛、i丁醛：醛，部2可包括例如：正丁醛、 乙基-1甲美/基—“庚嗣、3—甲基.庚醇、2-駿、2_ r装土戊酪、2 一乙基一 4 —甲基戊醇、2-乙基己 • 2 —乙基己烯醛、2 -乙基己-3 -烯醇、2 —乙基己醇 /一 基丁酸醋、2 —乙基己基—2 —乙基己酸醋、 匕土班酸、2 一乙基己一 L3 一二醇、環C12二醇、環C12 内酯、環飽和及不飽和k醚類、q醚類、正丁基—2_乙基 己鱗，以及三聚正丁醛。 此種有機化合物在水性媒質内的濃度，習慣上是以 COD值稱之。c〇D值（此c〇D縮寫指化學氧需要量）是以氧 當量表示的重鉻酸鉀量，由1公升水的氧化性成份所消耗 者 COD值是以標準化程序所決定，載於例如uiimanns& 《工業化學百科》第4版（1981)，第4卷376頁起。 在廢水可以引入習知處理廠、河道或其他承受水體之 刚’其有機雜質含量必須明顯降低，以符合廢水内最大污 574146 五、發明說明（4) 染物濃度的法定嚴格要求。 EP A-0 631 988揭示一種製法，可大幅降低醇醛化和 隨後加氫反應所得廢水中有機雜質之濃度。 在此製法中，將上述三種廢水部份合併，調節呈pH 0 - 6。然後，視需要把分離的有機相除去，而廢水再用分 子内含Cs或以上的單元醇和/或分子内含q以上的烴萃取。 此法在工業上可簡單進行，並可將合併廢水内存在的 有機化合物除去至少90%。 經萃取後存在並加載有機化合物和副產品的萃取媒質 ，在實務條件下，經蒸餾回收。所得蒸餾殘渣和墓餾挞頂·· 取出的部份’包括主要的有機副產品，並供應熱用、途^ 由侧面取出回收的萃取媒質再循環至萃取製程，並補 加萃取媒質。 ΕΡ-Α-0 63 1 988製法的重要目的，在於調節一般鹼性 廢水至pH 0 - 6，尤其是卜3。使羧酸質子化，例如呈水溶 性鹼金屬鹽存在，因而轉變成游離羧酸。此等游離酸 水溶性物質。因而多多少少發展成有機相，從廢水除去， 業已達成-定程度的COD值下降。設定該pH亦造成萃 質在水中的溶解度進一步降低。i因已知萃取媒質在水中 的溶解度有pH依賴&，在酸性媒質内較在鹼性媒質内 降低。所以，在酸性溶液内，對c〇D值的增加只小有貢 然EP-A-〇 631 合物外，仍包括 儘管pH降低後接著除去所得有機相， 988製法内的廢水除溶化的水溶性有機化 574146 五、發明說明（5) -定量的非水溶性有機化合物，在廢水中乳化 即不能從廢水除去，直到pH調節後的萃取步驟。=質 載此等雜質的萃取媒質蒸餾必須使用高溫卒==裝 !增加形成高沸點縮合生成物。為： 大ΐ的：顧二在條：下，從蒸館反應器連續取出： 的…餾底相。然而，母次也會附帶除去2_ :而從再循環中損失。意即在蒸館下游再 U己 醇，必須不斷補充新加的2_乙基己醇。 乙基己 本發明之㈣’在於提供一種醇酸化和下游加 風斤传廢水之改良淨化方法’得以更有效回收萃取媒 ^的係以製造醇類所得廢水的淨化方法達成，、此製 乂匕括醇醛化反應，接著加氫，最後的 含有三部份： 哔為餾，此專廢水 (1) 醇醛化反應所得含觸媒水相 (2) 醇醛化製成α，冷—不飽和醛精製所得洗水 (3 )醇蒸顧殘渣淨化所得洗水 =併的廢水部份是用含c8_Ci6W元醇和/或分子 内s C6-Cu的煙萃取，此方法包括：Page 6 V. Description of the invention (3) Acids In this case, the following may be produced by a very small amount of by-products. • Produced by aldolization ^ 7 ο J. Mouth exists ... One more carbon ^ ^ ^ The required alcohol is one or two carbon atoms less lactones and acids. ,, branched alcohols, aldehydes, ethers, in addition, waste k products, and boiling point = Γ, including aerated products from the alcohol by-products of the reaction, if 2 ethyl I is still a condensation product. And then add 3 ΐ: 酿: isobutyraldehyde, i-butyraldehyde: aldehyde in the presence of sodium hydroxide solution, Part 2 may include, for example: n-butyraldehyde, ethyl-1 meme / yl-"heptyl" , 3-methyl.heptanol, 2-Jun, 2-r packed with pentamyl, 2-ethyl-4-methylpentanol, 2-ethylhexyl 2-ethylhexenal, 2-ethyl Hex-3-enol, 2-ethylhexanol / monobutyric acid vinegar, 2-ethylhexyl-2-ethylhexanoic acid vinegar, dextrin acid, 2-ethylhexyl-L3 monodiol, Ring C12 diols, ring C12 lactones, ring-saturated and unsaturated k-ethers, q-ethers, n-butyl-2-ethylhexyl scale, and tri-n-butyraldehyde. The organic compounds in aqueous media The concentration is customarily referred to as the COD value. The coD value (the abbreviation for COD refers to the chemical oxygen demand) is the amount of potassium dichromate expressed in oxygen equivalent, consumed by the oxidizing component of 1 liter of water The COD value is determined by standardized procedures and is contained in, for example, uiimanns & Encyclopedia of Industrial Chemistry, 4th edition (1981), vol. 4, page 376. Wastewater can be introduced into conventional treatment plants, rivers or other rigid bodies that bear water. ' Organic miscellaneous The content must be significantly reduced to comply with the maximum pollution in wastewater 574146 V. Description of the invention (4) Strict legal requirements for the concentration of dyes. EP A-0 631 988 discloses a manufacturing method that can significantly reduce the waste water obtained from aldolization and subsequent hydrogenation reactions. Concentration of organic impurities. In this production method, the above three types of wastewater are combined to adjust the pH to 0-6. Then, the separated organic phase is removed as necessary, and the wastewater is reused with a unit alcohol containing Cs or more in the molecule and / Or the extraction of hydrocarbons containing more than q in the molecule. This method can be easily carried out industrially, and can remove at least 90% of the organic compounds present in the combined wastewater. The extraction medium that is present and loaded with organic compounds and by-products after extraction is practical Under the conditions, it is recovered by distillation. The obtained distillation residue and tomb tartar top ... The part taken out includes the main organic by-products and is supplied for heating and use. The extraction medium recovered from the side is recycled to the extraction process and replenished. Add the extraction medium. The important purpose of the EP-A-0 63 1 988 production method is to adjust the general alkaline wastewater to pH 0-6, especially Bu 3. Protonate the carboxylic acid. For example, it is present as a water-soluble alkali metal salt, so it is converted into free carboxylic acid. These free acids are water-soluble substances. Therefore, they have developed into an organic phase more or less, and have been removed from wastewater. A certain degree of COD value has been reached. Set this pH It also causes the solubility of the extract in water to be further reduced. Because the solubility of the extraction medium in water is pH-dependent, it is lower in acidic media than in alkaline media. Therefore, in acidic solutions, The increase of the value is only a small amount of Gongran EP-A-〇631 compound, and it still includes the water-soluble organic chemical that removes and dissolves the wastewater in the 988 production method despite the decrease in pH and subsequent removal of the organic phase. 574146 5. Description of the invention (5) -A quantitative amount of water-insoluble organic compounds that cannot be removed from the wastewater by emulsification in the wastewater until the extraction step after pH adjustment. = Distillation of the extraction medium containing these impurities must be performed at high temperatures. == Add to increase the formation of high-boiling condensation products. For: Dasao's: Gu Er under the bar: Continuously take out: from the distillation bottom reactor. However, the mother and child will also be removed by 2_: and lost from recycling. This means that U-Hexanol must be replenished continuously in the downstream of the steaming hall. Ethyl ether of the present invention 'is to provide an improved purification method of alcohol acidification and downstream air-borne waste water purification', which can more effectively recover the extraction medium and achieve the purification method of wastewater obtained from the production of alcohol. Including the aldolization reaction, followed by hydrogenation, the final contains three parts: Beep is distillation, this special wastewater (1) the catalyst-containing aqueous phase obtained from the aldolization reaction (2) aldolization to α, cold-no The washing water (3) obtained from the purification of saturated aldehydes is purified by alcohol distillation and the residue is purified. The waste water obtained is purified by extraction with smoke containing c8_Ci6W alcohol and / or intramolecular s C6-Cu.

(a) 在萃取上游，先將三部份廢水至少其二合併， 調節至pH 0-6，如有需要除去此時形有機 相， (b) 在製程中，令三部份廢水之—或以上個別和/ 集體與聚結濾材接觸。(a) upstream of the extraction, first combine at least two of the three parts of wastewater, adjust to pH 0-6, if necessary, remove the organic phase at this time, (b) in the process, make the three parts of wastewater—or The above individually and / or collectively come into contact with the coalescing filter media.

574146 五、發明說明（6) ^ 本發明方法所用醇類製造（包括醇醛化反應，接著加 氣’最後醇蒸餾）所得廢水，為三部份（1 ，可包 括水溶性和非水溶性有機化合物，業已詳細特定如上。 。本發明方法中所用聚結濾材為極細除霧用液/液相分 離器’其中聚結物理作用是在特別構成的圓筒形纖維床元 件内實施。此種聚結濾材在前案中已知（例如參見《化學 技術》18 (1989)， 14-21)。例如包含聚丙烯或聚四氟乙 烯的塑膠纖維、玻璃纖維或金屬纖維。流經纖維床必須有 大約0 · 1巴的驅動差壓。 性有機 離層扣 出π， 此有機 廢水， 的有機 量的有 即相對 減少形 連續除 損失， ’在萃 加萃取 在574146 V. Description of the invention (6) ^ The waste water produced by the alcohol used in the method of the present invention (including aldolization reaction, followed by aeration and final alcohol distillation) is a three-part (1, which can include water-soluble and non-water-soluble organic The compounds have been specified in detail as above. The coalescing filter used in the method of the present invention is a liquid / liquid phase separator for extremely fine defogging, wherein the coalescing physical effect is performed in a specially constructed cylindrical fiber bed element. Such coalescing Knotting media are known in previous cases (see, for example, Chemical Technology 18 (1989), 14-21). For example, plastic fibers, glass fibers, or metal fibers containing polypropylene or polytetrafluoroethylene. Flow through the fiber bed must have The driving differential pressure is about 0.1 bar. The organic organic layer deducts π, and the organic amount of this organic wastewater has a relatively reduced continuous removal loss.

經聚結濾材的纖維床時，微細分散於廢水内的非才 化合物即合併，或被業已存在於纖維床上的有機会 持，形成潤濕膜。此膜隨同驅動廢水流移到纖維身 在此間歇分離大滴有機相，並單獨因重力而分離。 可從廢水分離，以致事實上進入後續萃取^ 2 f低⑽值’故在萃*中的衫，只有較少量 須除去，•開萃取的萃取媒質只承載較少 庫較二；：ί:反應器内回收萃取媒質所需溫肩 :二 媒質利用蒸顧作業中，侧When coalescing the fiber bed of the filter medium, the non-performing compounds finely dispersed in the waste water are merged or are held by the opportunity already existing on the fiber bed to form a wetting film. This membrane drives the wastewater to the fiber body, where large drops of organic phase are separated intermittently and separated by gravity alone. It can be separated from waste water, so that it will actually enter the subsequent extraction ^ 2 f low threshold value. Therefore, only a small amount of the shirt in the extraction * must be removed. • The extraction medium that opens the extraction only carries fewer reservoirs than the second one: ί: The warm shoulder needed to recover the extraction medium in the reactor:

i更點的副產品。s此，只有少量蒸顧底相! 去…果，不用聚結濾材時，萃取媒f# f& 明顯較EP —A-Ο 631 988之：：媒；在作業" 取媒質利用蒸餾作業後，.4f :鹿附帶優點邊 媒質。 ^兩添加明顯更少量的杂 本發明方法中’聚結濾材的中間關聯，提供一㈣ 五、發明說明（8) 醇類。可d::萃取媒質，使用分子内|有c c的 ϊ:萃取媒質亦包i;構飽和’不必用：醇類、。 已證明有用的是2_乙基己醇不门'子大小醇類之混 '、辛知、壬醇、癸醇 ，5, 5~三甲基己醇、 癸醇之混合物。 、力知，以及異構性辛醇、壬醇和 除醇類外，分子内有Γ Γ J亦可為直鍵或支鏈、;和可用做萃取媒質 的疋石油（特別是輕燃油）苯 2和。已證明特別有用 烴之混合物。 、 …、 製成低沸點部份的不同 除醇此口物或不同煙之混合 物亦可用來從廢水萃取有機化合物一；類和煙類的混合 圍，主要受到諸成份溶混性的限制。：：：：延伸到廣範 或烴類已證明為特定廢水中通常： ：：：酵類和/ 取媒質。其只能被水相溶Λ的有機物理之優異萃 有機化合物是利為重點。 置内，從廢水萃取，已證明有用的三在溶劑萃取常用的裝 級，形成複數此合器〜沉析器彼此成飞夕 理’可用具有靜態内部之萃取拔 萃取..且。同 動内部者，諸如授拌塔、萃取媒質充塔’或具有活 好是逆流傳導。 萃取媒質和载體液係順流，或更 萃取媒質可以“簡單方式再生 蒸德殘渔；；：：：出料包括要除去的有機化合物：至 熱用途，而萃取媒質則藉塔側出料回收，再循環至萃取製 — -----—-— __ 第12頁 574146 五、發明說明（9) 程。 本發明新法適用於處理醇醛化反應和下 ’與採取的醇醛化方法及所用原料1關。'σ風、二 叮…、開所以，醇醛化可 例如以驗金屬氣氧化物、驗土金屬碳酸鹽或胺，做為觸媒 ，以及用醛類或酮類進行。 €0 第1圖：ΕΡ-6：3 1 988號（不用聚結濾材）的實施例流程圖 第2圖：本案請求製法（含聚結濾材）實施例之流程圖 ipi more point by-products. s Here, only a small amount of steam is used to get the bottom phase! To ... If the filter medium is not agglomerated, the extraction medium f # f & is significantly better than EP —A-Ο 631 988 :: Medium; after the operation " Distillation operation of the medium extraction, .4f: Deer side merit medium. ^ Two additions of significantly smaller amounts of impurities are added in the middle of the method of the present invention, to provide an explanation of the invention (8) alcohols. May d :: extraction medium, use intramolecular | with c c ϊ: extraction medium also includes i; structure saturation 'need not be used: alcohols. It has proven useful to be a mixture of 2-ethylhexanol, 'sub-size alcohols', octane, nonanol, decanol, 5, 5-trimethylhexanol, and decanol. , Lizhi, as well as isomeric octanol, nonanol, and alcohols, Γ Γ J in the molecule can also be a straight or branched chain; and osmium oil (especially light fuel oil) benzene that can be used as an extraction medium 2 with. Mixtures of hydrocarbons have proven particularly useful. …… Make different low-boiling point parts. In addition to alcohol, this mouthpiece or a mixture of different smoke can also be used to extract organic compounds from wastewater. The mixing range of types and smoke is mainly limited by the miscibility of the ingredients. :::: extended to a wide range or hydrocarbons that have proven to be in specific wastewaters usually: :::: ferments and / mediators. It can only be extracted with excellent organic physics from water-soluble organic compounds. It can be used for extraction from waste water. It has been proven to be useful in solvent extraction. It is commonly used in solvent extraction to form a plurality of combiners and decanters to form each other. It can be used for extraction with a static interior. Synchronous insiders, such as mixing towers, extraction media filling towers' or have active countercurrent conduction. The extraction medium and the carrier liquid are co-current, or the extraction medium can "regenerate the steamed fishery in a simple way ;; ::: the output includes the organic compounds to be removed: for thermal use, and the extraction medium is recovered by the tower side discharge. Recycling to the extraction system ------------ __ Page 12 574146 V. Description of the invention (9) process. The new method of the present invention is suitable for treating the aldolization reaction and the method used and the used aldolization method. Raw material 1 off. 'Σ wind, diding ..., on. Therefore, aldolization can be performed, for example, with metal oxides, soil metal carbonates or amines as catalysts, and with aldehydes or ketones. € 0 Figure 1: EP-6: 3 1 988 (without coalescing filter material) embodiment flow chart Figure 2: This case request method (including coalescing filter material) embodiment flow chart ip

第13頁Page 13

Claims (1)

574146 17121381 … τ項·号π乾圍 ------ 处:u Ϊ的有機相釋出’再將剩餘廢水與章已傳邋、s 者。.如申請專利範圍第5項之方法，其中ρΗ範圍為卜3 (31 專利範圍第1項之方法，其中廢水部份（1U )先按々步驟（a)彼此合併，調至pH 〇 — 6，可親+ i 和 將混合物送往萃取 其中pH範圍為卜3 其中先將全部三部 必要時從形成的有 ’付諸萃取者。 其中pH範圍為卜3 其中P Η是利用鹽 5的有機相釋出，並通過聚結渡#，剩餘廢水再：巧： 樣通過聚結濾材的廢水部份（2 )合併· μ ”業已同 者。 8 ·如申請專利範圍第7項之方法： 者。 9 ·如申請專利範圍第1項之方法5 份廢水（1 ) ( 2 ) ( 3 )合併，調節pH 〇 — 6， 機相釋出，再集體傳導通過聚結濾材 I 0 ·如申請專利範圍第9項之方法， 者。 II ·如申請專利範圍第1項之方法， 酸、硫酸、硝酸或磷酸調節者。 第15頁 2003.10. 27.015 574146574146 17121381… item τ · No. π dry perimeter ------ place: u Ϊ organic phase is released ’and then the remaining waste water and chapter have been passed on, s. . If the method of applying for the scope of the patent No. 5 item, wherein the range of ρΗ is Bu 3 (31 of the patent scope No. 1 method, wherein the wastewater parts (1U) are first combined with each other according to step (a) and adjusted to pH 〇-6 , Can be affinity + i and send the mixture to extraction where the pH range is bu 3 which will first put all three if necessary from the formed with 'extractor'. Where pH range is bu 3 where P Η is organic using salt 5 The phase releases and passes through the coalescence crossing #, and the remaining waste water is again: Qiao: The waste water portion (2) that is passed through the coalescing filter material has been merged. Μ "has the same. 8 · If the method of the scope of patent application No. 7: 9 · If method 5 of the scope of patent application is applied, 5 parts of waste water (1) (2) (3) are combined to adjust the pH 〇-6, the organic phase is released, and then collectively conducted through the coalescing filter material I0. The method of the scope of the item 9, II. The method of the scope of the patent application, the regulator of the acid, sulfuric acid, nitric acid or phosphoric acid. Page 15 2003.10. 27.015 574146 具體例A2還是包括先將廢水部份（1)和（3)按照步驟 成6^古她口併調節到PH 〇 _ &，以1 _ 3為佳，並視需要從形 成：：機相釋出，再將剩餘廢水與業已傳導通過聚結濾材 的廢水部份（2 )合併，將混合物送往萃取。 在具體例A3内，廢水部份（1)和（3)先按照步驟（㈧彼 此口併，調至pH 〇-6，以1-3為佳，可視需要從形成的有 機相釋出，並通過聚結濾材，剩餘廢水再與業以同樣通過 聚結濾材的廢水部份（2)合併，將混合物送往萃取。 又一具體例A4的特點是，事實上先將全部三部份廢水 (1)(2)(3)合併，調節pH 〇 — 6,以卜3為佳，必要時從形成 的有機相釋出，再集體傳導通過聚結濾材，付諸萃取。 為設定廢水的pH，使用鹽酸、硫酸、硝酸、磷酸等無 機酸，以硫酸為佳。 因為固體粒定著於聚結濾材之纖維床内，會有損分離 效率，宜在聚結濾材上游連接通當濾材階段，以除去固定 粒0The specific example A2 still includes firstly adjusting the wastewater (1) and (3) into 6 ^ guta mouth and adjusting it to pH 〇_ &, preferably _3, and forming from: After the release, the remaining wastewater is combined with the wastewater portion (2) that has been conducted through the coalescing filter, and the mixture is sent for extraction. In the specific example A3, the waste water parts (1) and (3) are firstly adjusted in accordance with the steps (to be adjusted to pH 0-6, preferably 1-3, and may be released from the formed organic phase as needed, and Through the coalescing filter medium, the remaining wastewater is then combined with the wastewater portion (2) that also passes through the coalescing filter medium, and the mixture is sent to the extraction. Another specific example A4 is characterized in that all three parts of the wastewater are in fact first ( 1) (2) (3) Combine and adjust the pH 〇-6, preferably bu 3, if necessary, release from the formed organic phase, and then collectively conduct it through the coalescing filter medium and extract it. To set the pH of the wastewater, Inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are used, and sulfuric acid is preferred. Because the solid particles are fixed in the fiber bed of the coalescing filter medium, the separation efficiency will be impaired. It should be connected to the filter medium upstream of the coalescing filter medium to Remove fixed particles 0 第11頁 2000.10.26.0Π 574146 < 案號 87121381 曰 9;ί·$αΛ3 $ 修正 申請專利範圍 | --------- 、 | 1 · 一種製造醇類所得廢水的淨化方法，此製造包括醇 醛化反應，接著加氫，最後的醇蒸餾一…‘ 份： (1) 醇醛化反應所得含觸媒水相 (2) 醇醛化製成α，召-不飽和醛精製所得洗水 (3 )醇蒸餾殘渣淨化所得洗水 此方法包括： (a)先將三部份廢水至少其二合併，調節至pH 〇 ’如 需要除去此時形成的有機相， 七隹雜（rtb)在製程中，令三部份廢水之一或以上個別和/ 或集體與聚結渡材接觸，最後 U / 而該合Ϊ)的將份廢水合併’並把渡合物進料至萃取， 分子内=、，水D卩份是用分子内含CVCu的單元醇和/或 2 广C〗2的烴加以萃取者。 者。·如申請專利範圍第}項之方法，其中邱範圍為卜3 要從形成的有機相耧屮 /併，調節至ρΗ ο-6，可视需 4·過？結濾材，再付、諸萃取者。 者。 明1靶圍第3項之方法，其中pH範圍為卜3 (1)和5 (5二請專利範圍第1項之方法，豆中先將麼水二 按照步驟（） 次无肘潑水部份 la)彼此a併，調節到ρΗ 〇 —6， 六 部Page 11: 2000.10.26.0Π 574146 < Case No. 87121381 9; ί · $ αΛ3 $ Amends the scope of patent application | ---------, | 1 · A purification method for wastewater from alcohol production, this The production includes an aldolization reaction, followed by hydrogenation, and the final alcohol distillation is one ... 'parts: (1) the catalyst-containing aqueous phase obtained from the aldolization reaction; (2) aldolization to α, and the unsaturated aldehyde purification obtained Washing water (3) Washing water obtained by purification of alcohol distillation residues. This method includes: (a) combining at least two of the three wastewaters first and adjusting the pH to 0; if necessary, remove the organic phase formed at this time, rtb ) In the process, one or more of the three wastewaters are individually and / or collectively contacted with the coalesced ferrous material, and finally the combined wastewater is combined and the ferrate is fed to the extraction. The internal water content is extracted with a unit alcohol containing CVCu in the molecule and / or a hydrocarbon with a wide range of carbon dioxide. By. · For the method of applying for the scope of the patent, item}, in which Qiu's scope is Bu 3, and the organic phase to be formed should be adjusted to ρΗ ο-6, as required. Knot the filter material, and then pay the extractors. By. The method of item 3 in the Ming 1 target, in which the pH range is 3 (1) and 5 (5) The method of item 1 in the patent range, the bean is firstly subjected to the step () and the elbow is splashed without water la) a and each other, adjusted to ρΗ 〇-6, six